Solubility Equilibrium - Definitions

Definitions

A solubility equilibrium exists when a chemical compound in the solid state is in chemical equilibrium with a solution of that compound. The equilibrium is an example of dynamic equilibrium in that some individual molecules migrate between the solid and solution phases such that the rates of dissolution and precipitation are equal to one another. When equilibrium is established, the solution is said to be saturated. The concentration of the solute in a saturated solution is known as the solubility. Units of solubility may be molar (mol dm−3) or expressed as mass per unit volume, such as μg ml−1. Solubility is temperature dependent. A solution containing a higher concentration of solute than the solubility is said to be supersaturated. A supersaturated solution may be induced to come to equilibrium by the addition of a "seed" which may be a tiny crystal of the solute, or a tiny solid particle, which initiates precipitation.

There are three main types of solubility equilibria.

  1. Simple dissolution.
  2. Dissolution with dissociation. This is characteristic of salts. The equilibrium constant is known in this case as a solubility product.
  3. Dissolution with reaction. This is characteristic of the dissolution of weak acids or weak bases in aqueous media of varying pH.

In each case an equilibrium constant can be specified as a quotient of activities. This equilibrium constant is dimensionless as activity is a dimensionless quantity. However, use of activities is very inconvenient, so the equilibrium constant is usually divided by the quotient of activity coefficients, to become a quotient of concentrations. See equilibrium chemistry#Equilibrium constant for details. Moreover, the concentration of solvent is usually taken to be constant and so is also subsumed into the equilibrium constant. For these reasons, the constant for a solubility equilibrium has dimensions related to the scale on which concentrations are measured. Solubility constants defined in terms of concentrations are not only temperature dependent, but also may depend on solvent composition when the solvent contains also species other than those derived from the solute.

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